- Determination on the binding of thiadiazole derivative to human serum albumin: a spectroscopy and computational approach
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4-[3-acetyl-5-(acetylamino)-2,3-dihydro-1,3,4-thiadiazole-2-yl]phenyl benzoate from the family of thiadiazole derivative has been newly synthesized. It has good anticancer activity as well as antibacterial and less toxic in nature, its binding characteris
- Karthikeyan, Subramani,Bharanidharan, Ganesan,Mani, Karthik Ananth,Srinivasan, Narasimhan,Kesherwani, Manish,Velmurugan, Devadasan,Aruna, Prakasarao,Ganesan, Singaravelu
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- Electrochemical Aerobic Oxidative Cleavage of (sp3)C-C(sp3)/H Bonds in Alkylarenes
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An electrochemistry-promoted oxidative cleavage of (sp3)C-C(sp3)/H bonds in alkylarenes was developed. Various aryl alkanes can be smoothly converted into ketones/aldehydes under aerobic conditions using a user-friendly undivided cell setup. The features of air as oxidant, scalability, and mild conditions make them attractive in synthetic organic chemistry.
- Liu, Shuai,Liu, Zhong-Quan,Shen, Tong,Shen, Xu,Wang, Nengyong,Wu, Jintao,Yang, Le,Zhao, Jianyou
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p. 3286 - 3295
(2022/03/14)
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- Energy-Transfer-Mediated Photocatalysis by a Bioinspired Organic Perylenephotosensitizer HiBRCP
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Energy transfer plays a special role in photocatalysis by utilizing the potential energy of the excited state through indirect excitation, in which a photosensitizer determines the thermodynamic feasibility of the reaction. Bioinspired by the energy-transfer ability of natural product cercosporin, here we developed a green and highly efficient organic photosensitizer HiBRCP (hexaisobutyryl reduced cercosporin) through structural modification of cercosporin. After structural manipulation, its triplet energy was greatly improved, and then, it could markedly promote the efficient geometrical isomerization of alkenes from the E-isomer to the Z-isomer. Moreover, it was also effective for energy-transfer-mediated organometallic catalysis, which allowed realization of the cross-coupling of aryl bromides and carboxylic acids through efficient energy transfer from HiBRCP to nickel complexes. Thus, the study on the relationship between structural manipulation and their photophysical properties provided guidance for further modification of cercosporin, which could be applied to more meaningful and challenging energy-transfer reactions.
- Zhang, Yan,Xia, Mingze,Li, Min,Ping, Qian,Yuan, Zhenbo,Liu, Xuanzhong,Yin, Huimin,Huang, Shuping,Rao, Yijian
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p. 15284 - 15297
(2021/11/01)
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- Metal-Free Selective Modification of Secondary Amides: Application in Late-Stage Diversification of Peptides
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Here we solve a long-standing challenge of the site-selective modification of secondary amides and present a simple two-step, metal-free approach to selectively modify a particular secondary amide in molecules containing multiple primary and secondary amides. Density functional theory (DFT) provides insight into the activation of C-N bonds. This study encompasses distinct chemical advances for late-stage modification of peptides thus harnessing the amides for the incorporation of various functional groups into natural and synthetic molecules.
- Adebomi, Victor,Sriram, Mahesh,Streety, Xavier,Raj, Monika
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supporting information
p. 6189 - 6193
(2021/08/01)
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- Mechanically induced solvent-free esterification method at room temperature
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Herein, we describe two novel strategies for the synthesis of esters, as achieved under high-speed ball-milling (HSBM) conditions at room temperature. In the presence of I2 and KH2PO2, the reactions afford the desired esterification derivatives in 45% to 91% yields within 20 min of grinding. Meanwhile, using KI and P(OEt)3, esterification products can be obtained in 24% to 85% yields after 60 min of grinding. In addition, the I2/KH2PO2 protocol was successfully extended to the late-stage diversification of natural products showing the robustness of this useful approach. Further application of this method in the synthesis of inositol nicotinate was also discussed. This journal is
- Zheng, Lei,Sun, Chen,Xu, Wenhao,Dushkin, Alexandr V.,Polyakov, Nikolay,Su, Weike,Yu, Jingbo
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p. 5080 - 5085
(2021/02/05)
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- General Paradigm in Photoredox Nickel-Catalyzed Cross-Coupling Allows for Light-Free Access to Reactivity
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Self-sustained NiI/III cycles are established as a potentially general paradigm in photoredox Ni-catalyzed carbon–heteroatom cross-coupling reactions through a strategy that allows us to recapitulate photoredox-like reactivity in the absence of light across a wide range of substrates in the amination, etherification, and esterification of aryl bromides, the latter of which has remained, hitherto, elusive under thermal Ni catalysis. Moreover, the accessibility of esterification in the absence of light is especially notable because previous mechanistic studies on this transformation under photoredox conditions have unanimously invoked energy-transfer-mediated pathways.
- Nocera, Daniel G.,Qin, Yangzhong,Sun, Rui
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supporting information
p. 9527 - 9533
(2020/04/08)
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- Visible-light-promoted site-specific and diverse functionalization of a c(sp3)-c(sp3) bond adjacent to an arene
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We report here a strategy for inert C-C bond functionalization. Site-specific cleavage and functionalization of a saturated C(sp3)-C(sp3) bond via a visible-light-induced radical process have been achieved. The general features of this reaction are as follows. (1) Both linear and cyclic C(sp3)-C(sp3) bonds with a vicinal arene can be specifically functionalized. (2) One carbon is converted into a ketone, and another can be tunably converted into nitrile, peroxide, or halide. (3) The typical conditions include 1.0 mol % of Ru(bpy)3Cl2, 1.0 or 5.0 equiv of Zhdankin reagent, white CFL (24 W), open flask, and room temperature. These reactions offer powerful tools to modify carbon skeletons that are intractable by conventional methods. Good selectivity and functional group tolerance, together with mild and open air conditions, make these transformations valuable and attractive.
- Fang, Fang,Liu, Zhong-Quan,Sun, Minzhi,Wang, Nengyong,Wang, Yaxin,You, Huichao,Zhao, Jianyou
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p. 6603 - 6612
(2020/07/27)
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- Palladium-Catalyzed Aerobic Oxidative Coupling of Amides with Arylboronic Acids by Cooperative Catalysis
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The first fluoride and palladium co-catalyzed conversion of amide to ester through an aerobic oxidative coupling pathway is reported. This new approach presents a practical process that employs easily available oxygen and commercially available arylboronic acids as coupling partners, uses a wide range of N- tosylamides, and proceeds under mild reaction conditions. This protocol demonstrates broad functional group tolerance, and provides an alternative option to synthesize esters from N-tosylamides which obtained by simply N-functionalization of secondary amides.
- Li, Yue,Wu, Hongxiang,Zeng, Zhuo
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p. 4357 - 4361
(2019/07/09)
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- Preparation method for synthesis of phenolic ester through thiocarboxylic acid mediated visible light catalyzed phenol acylation reaction
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The invention discloses a preparation method for synthesis of phenolic ester through a thiocarboxylic acid mediated visible light catalyzed phenol acylation reaction. Thiocarboxylic acid compounds andphenol compounds are subjected to a site specific reaction under certain conditions to produce phenolic ester compounds, wherein the certain conditions are as follows: under the conditions of normaltemperature, normal pressure and visible light, K2CO3 is used as an alkaline catalyst, terpyridyl ruthenium dichloride hexahydrate is used as a photosensitizer and acetonitrile is used as a reaction solvent. Synthesis of phenolic ester under catalysis of visible light is realized, thiocarboxylic acid is used as an acylation reagent, and the site specific phenol esterification reaction is realizedefficiently under mild conditions of normal temperature, normal pressure and visible light. The method has mild reaction conditions, large substrate functional group tolerance, high applicability andhigh yield, and an efficient, reliable and economical preparation method is provided for synthesis of phenolic ester.
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Paragraph 0017; 0018; 0065; 0066; 0067
(2018/07/30)
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- Transesterification of (hetero)aryl esters with phenols by an Earth-abundant metal catalyst
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Readily available and inexpensive Earth-abundant alkali metal species are used as efficient catalysts for the transesterification of aryl or heteroaryl esters with phenols which is a challenging and underdeveloped transformation. The simple conditions and the use of heterogeneous alkali metal catalyst make this protocol very environmentally friendly and practical. This reaction fills in the missing part in transesterification reaction of phenols and provides an efficient approach to aryl esters, which are widely used in the synthetic and pharmaceutical industry.
- Chen, Jianxia,Namila,Bai, Chaolumen,Baiyin, Menghe,Agula, Bao,Bao, Yong-Sheng
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p. 25168 - 25176
(2018/07/29)
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- Diacyl Disulfide: A Reagent for Chemoselective Acylation of Phenols Enabled by 4-(N,N-Dimethylamino)pyridine Catalysis
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A general and excellent acylation reagent, diacyl disulfide, was uncovered for efficient ester formation enabled by DMAP (4-(N,N-dimethylamino)pyridine) catalysis. This protocol offered a promising synthetic platform on site-selective acylation of phenolic and primary aliphatic hydroxyl groups, which greatly expanded the realm of protecting group chemistry. The importance of the reagent was also reflected by its excellent moisture tolerance, high efficiency, and potential in synthetic chemistry and biologically meaningful natural product modification.
- Liu, Hong-Xin,Dang, Ya-Qian,Yuan, Yun-Fei,Xu, Zhi-Fang,Qiu, Sheng-Xiang,Tan, Hai-Bo
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supporting information
p. 5584 - 5587
(2016/11/17)
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- Stereoselective synthesis of cis-2,6-disubstituted morpholines and 1,4-oxathianes by intramolecular reductive etherification of 1,5-diketones
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A simple and efficient, Lewis acid catalysed reductive etherification strategy for the stereoselective synthesis of cis-2,6- disubstituted morpholines and 1,4-oxathianes starting from readily available 1,5-diketones has been developed. The strategy is used in the total synthesis of morpholine-based natural products (±)-chelonin A and formal total synthesis of (±)-chelonin C.
- Gharpure, Santosh J.,Anuradha, Dandela,Prasad, Jonnalagadda V. K.,Rao, Pidugu Srinivasa
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supporting information
p. 86 - 90
(2015/01/16)
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- Synthesis of phenyl-1-benzoxepinols isolated from butcher's broom and analogous benzoxepines
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Extracts of Ruscus aculeatus L., known as butcher's broom, are mainly used for the treatment of chronic venous insufficiency (CVI). In a recent study on the phenolic compounds of Rusci rhizoma, new phenyl-1-benzoxepinols were isolated. As the therapeutic effect of butcher's broom is ascribed to the pharmacological activity of the main constituents, steroidal saponins and their aglycones the ruscogenins, the role of the newly identified compounds was of interest. Owing to the low availability of the compounds by isolation, we synthesized them for pharmacological testing. In an ORAC-fluorescein assay they revealed a significant antioxidative activity, which may contribute to the anti-inflammatory properties of the phenolic fraction obtained from Rusci rhizoma extracts. Copyright
- Herrmann, Josef M.,Untergehrer, Monika,Juergenliemk, Guido,Heilmann, Joerg,Koenig, Burkhard
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supporting information
p. 3170 - 3181
(2014/06/09)
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- Nucleophilic substitution reactions of Y-Substituted-Phenyl Benzoates with Potassium Ethoxide in Anhydrous Ethanol: Reaction Mechanism and Role of K+ Ion
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Pseudo-first-order rate constants (kobsd) have been measured spectrophotometrically for the reactions of Ysubstituted-phenyl benzoates (5a-j) with potassium ethoxide (EtOK) in anhydrous ethanol at 25.0 ± 0.1 °C. The plots of kobsd vs. [EtOK] curve upward regardless of the electronic nature of the substituent Y in the leaving group. Dissection of kobsd into the second-order rate constants for the reactions with the dissociated EtOV and ion-paired EtOK (i.e., kEtO-and kEtOK, respectively) has revealed that the ion-paired EtOK is more reactive than the dissociated Et-V. The Bronsted-type plots for the reactions with the dissociated Et-V and ion-paired EtOK exhibit highly scattered points with βlg = -0.5 ± 0.1. The Hammett plots correlated with ao constants result in excellent linear correlations, indicating that no negative charge develops on the O atom of the leaving Ysubstituted-phenoxide ion in transition state. Thus, it has been concluded that the reactions with the dissociated EtOV and ion-paired EtOK proceed through a stepwise mechanism, in which departure of the leaving group occurs after the RDS, and that K+ ion catalyzes the reactions by increasing the electrophilicity of the reaction center through a four-membered cyclic TS structure.
- Kim, Song-I,Cho, Hyo-Jin,Um, Ik-Hwan
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p. 177 - 181
(2014/02/14)
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- A general and efficient palladium-catalyzed alkoxycarbonylation of phenols to form esters through in situ formed aryl nonaflates
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Esters made easy! A general and efficient methodology for the palladium-catalyzed alkoxycarbonylation of in situ formed aryl nonaflates has been developed (see scheme). Both homo- and cross-esterifications are possible. DPPF=1,1′-bis(diphenylphosphino)ferrocene. Copyright
- Wu, Xiao-Feng,Neumann, Helfried,Beller, Matthias
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supporting information; experimental part
p. 3831 - 3834
(2012/05/20)
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- Kinetics and mechanism of nucleophilic displacement reactions of Y-substituted phenyl benzoates with cyanide Ion
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Second-order rate constants (kCN-) have been measured for nucleophilic substitution reactions of Y-substituted phenyl benzoates (1a-r) with CN- ion in 80 mol % H2O/20 mol % DMSO at 25.0 ± 0.1 °C. The Bronsted-type plot is linear with βlg = -0.49, a typical βlg value for reactions reported to proceed through a concerted mechanism. Hammett plots correlated with σo and σ-constants exhibit many scattered points. In contrast, the Yukawa-Tsuno plot for the same reaction exhibits excellent linearity with pY = 1.37 and r = 0.34, indicating that a negative charge develops partially on the oxygen atom of the leaving aryloxide in the rate-determining step (RDS). Although two different mechanisms are plausible (i.e., a concerted mechanism and a stepwise pathway in which expulsion of the leaving group occurs at the RDS), the reaction has been concluded to proceed through a concerted mechanism on the basis of the magnitude of βlg and pY values.
- Kim, Song-I,Kim, Eun-Hee,Um, Ik-Hwan
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experimental part
p. 689 - 693
(2010/08/19)
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- Cu(OTf)2-mediated Chan-Lam reaction of carboxylic acids to access phenolic esters
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A Cu(OTf)2-mediated Chan-Lam reaction of carboxylic acids with arylboronic acids is described. It represents a facile and practical methodology to access phenolic esters in moderate to good yields. The procedure tolerates a series of functional groups, such as methoxycarbonyl, acetoxy, free phenolic hydroxyl, vinyl, nitro, trifluoromethyl, methoxyl, bromo, chloro, iodo, and acetyl groups.
- Zhang, Lingli,Zhang, Guoying,Zhang, Manli,Cheng, Jiang
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experimental part
p. 7472 - 7474
(2011/01/03)
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- Aminolysis of Y-substituted phenyl X-substituted benzoates with piperidine: Effect of nonleaving group substituent
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The title reaction has been suggested to proceed through a zwitterionic tetrahedral intermediate with a change in the rate determining step on the basis of the curved Bronsted-type plots obtained. The curvature center of the curved Bronsted-type plots is at pKa = 6.4 regardless of the electronic nature of the substituent X in the benzoyl moiety.
- Um, Ik-Hwan,Lee, Ji-Youn,Ko, Seung-Hak,Bae, Sun-Kun
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p. 5800 - 5803
(2007/10/03)
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- Structure-reactivity correlations in nucleophilic substitution reactions of Y-substituted phenyl X-substituted benzoates with anionic and neutral nucleophiles
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A kinetic study is reported for the reactions of 4-nitrophenyl X-substituted benzoates (1a-l) and Y-substituted phenyl benzoates (2a-l) with two anionic nucleophiles (OH- and CN-) and three amines (piperidine, hydrazine, and glycylglycine) in 80 mol% H2O-20 mol% dimethyl sulfoxide (DMSO) at 25.0 ± 0.1 °C. Each Hammett plot exhibits two intersecting straight lines for the reactions of 1a-l with the anionic nucleophiles and piperidine, while the Yukawa-Tsuno plots for the same reactions are linear. The Hammett plots for the reactions of 2a-l with hydrazine and glycylglycine demonstrate much better linear correlations with σ- constants than with σ° or σ constants, indicating that the leaving group departure occurs at the rate determining step (RDS). On the contrary, σ- constants result in poorer Hammett correlation than σ° constants for the corresponding reactions with OH- and CN-, indicating that the leaving group departure occurs after the RDS for the reactions with the anionic nucleophiles. The large ρX value (1.7 ± 0.1) obtained for the reactions of 1a-l with the anionic nucleophiles supports the proposal that the reactions proceed through an addition intermediate with its formation being the RDS. The Royal Society of Chemistry 2006.
- Um, Ik-Hwan,Lee, Ji-Youn,Fujio, Mizue,Tsuno, Yuho
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p. 2979 - 2985
(2008/02/11)
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- Aminolysis of 2,4-dinitrophenyl X-substituted benzoates and Y-substituted phenyl benzoates in MeCN: Effect of the reaction medium on rate and mechanism
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Second-order rate constants (kN) have been determined spectrophotometrically for the reactions of 2,4-di-nitrophenyl X-substituted benzoates (1a-f) and Y-substituted phenyl benzoates (2a-h) with a series of alicyclic secondary amines in MeCN at
- Um, Ik-Hwan,Jeon, Sang-Eun,Seok, Jin-Ah
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p. 1237 - 1243
(2008/09/18)
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- Electrostatic catalysis by ionic aggregates: Scope and limitations of Mg(ClO4)2 as acylation catalyst
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Alkali and alkaline earth metal perchlorates exhibit electrostatic catalysis in the activation of anhydrides for the acylation reaction. Perchlorates with higher values of the charge-size function of the metal ion exhibit better catalytic activity following the order Mg(ClO4) 2>Ba(ClO4)2>LiClO4. Acylation of structurally diverse phenols, thiols, alcohols, and amines have been carried out with stoichiometric amounts of anhydride at room temperature under solvent free conditions in the presence of catalytic amount of Mg(ClO4) 2. Sterically hindered and electron deficient phenols are efficiently acylated. Acylation with sterically hindered anhydrides such as iso-butyric, pivalic, and benzoic anhydrides are carried out with phenols and alcohols in excellent yields. Acid-sensitive alcohols are acylated in excellent yields without any competitive side reactions.
- Chakraborti, Asit K.,Sharma, Lalima,Gulhane, Rajesh,Shivani
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p. 7661 - 7668
(2007/10/03)
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- Studies of reactions within molecular complexes: Alkaline hydrolysis of substituted phenyl benzoates in the presence of xanthines
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Complexation with caffeine and theophylline-7-acetate depresses the rate of alkaline hydrolysis of substituted phenyl benzoates and is consistent with the formation of molecular complexes with 1:1 stoichiometry between the hosts and esters; stacking of the xanthines is excluded as an explanation in the range of concentrations studied. Bronsted-type correlations have been determined for the rate and complexation constants and for the transition-state binding constants. Development of effective charge in the transition state of the reactions in bulk solvent is slightly less than that in the host-ester complex, consistent with a similar electronic environment in both states. The negative Bronsted β values for Ks indicate that the interactions between ester and hosts involve electron donation to the host from the ester. Inhibition of hydrolysis is attributed to repulsion of the hydroxide ion from the host-ester complex by the extra hydrophobicity engendered by the xanthine host, as well as by the weaker binding of the transition state to the host compared with that in the host-ester complex.
- Pirinccioglu, Necmettin,Williams, Andrew
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- Oxidative deoximation with sodium perborate
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An efficient and convenient conversion of oximes to corresponding carbonyl compounds with sodium perborate in glacial acetic acid is reported.
- Bandgar,Shaikh,Iyei, Suresh
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p. 1163 - 1168
(2007/10/03)
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- Liquid crystal compounds having chiral ester head groups
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Liquid crystal compounds which show a ferroelectric phase and which exhibit high spontaneous polarization values and smectic behavior over a range of temperatures have the formula STR1 wherein R1 is alkyl of from 1 to 16 carbon atoms; alkoxy; haloalkyl; alkoxyalkyl, wherein the alkoxy substituent thereof comprises a chain of carbon atoms including one or more oxygen ether atoms; or alkoxyalkoxy, wherein the alkoxy substituent thereof comprises a chain of carbon atoms including one or more oxygen ether atoms; R2 is alkyl of from 1 to 4 carbon atoms; each of R3 and R4 is alkylene; n is an integer 1 or 2; and W is alkyl of from 1 to 12 carbon atoms or fluoroalkyl of the formula STR2 wherein each of X, Y and Z is hydrogen or fluorine, m is zero or an integer from 1 to 6, and at least one of X, Y and Z is fluorine when m is zero.
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